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Closo- or Nido-Carborane Diphosphane as Responsible for Strong Thermochromism or Time Activated Delayed Fluorescence (TADF) in [Cu(N^N)(P^P)]0/+
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-11-23 , DOI: 10.1021/acs.inorgchem.1c03092 Adrián Alconchel 1 , Olga Crespo 1 , Pilar García-Orduña 1 , M Concepción Gimeno 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-11-23 , DOI: 10.1021/acs.inorgchem.1c03092 Adrián Alconchel 1 , Olga Crespo 1 , Pilar García-Orduña 1 , M Concepción Gimeno 1
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Ortho-closo or ortho-nido-carborane-diphosphanes have been selected to prepare the heteroleptic cationic or neutral [Cu(N^N){(PPh2)2C2B10H10}]PF6 (1) and [Cu(N^N){(PPh2)2C2B9H10}] (2) [N^N = 2-(4-thiazolyl)benzimidazole], respectively. Complexes 1 and 2 display very different emissive behavior. Neutral complex 2 exhibits TADF (time activated delayed fluorescence) which has been studied both as powder and PMMA composite with similar ΔE(S1 – T1), τ(T1), and τ(S1) in both phases. Cationic complex 1 displays a much lower quantum yield than 2 and does not show TADF, but it exhibits a significant thermochromic luminescence, and its emission is very dependent on the medium. Theoretical studies show that metal–ligand (M–diphosphane) to ligand (L′, diimine) transitions, MLL′CT, are responsible of the transitions which originate the emissive properties, but with very different contribution of the copper center, carborane cluster, and diphosphane phenyl rings for 1 and 2.
中文翻译：
Closo- 或 Nido-Carborane Diphosphane 负责 [Cu(N^N)(P^P)]0/+ 中的强热致变色或时间激活延迟荧光 (TADF)
选择邻位或邻位碳硼烷二膦来制备杂配阳离子或中性 [Cu(N^N){(PPh 2 ) 2 C 2 B 10 H 10 }]PF 6 ( 1 ) 和 [Cu (N^N){(PPh 2 ) 2 C 2 B 9 H 10 }] ( 2 ) [N^N = 2-(4-噻唑基)苯并咪唑]。配合物1和2显示出非常不同的发射行为。中性复合物2表现出 TADF（时间激活延迟荧光），已作为粉末和 PMMA 复合材料进行研究，在两相中具有相似的 Δ E (S 1 – T 1 )、τ(T 1 ) 和 τ(S 1 )。阳离子配合物1表现出比2低得多的量子产率并且不显示TADF，但它表现出显着的热致变色发光，并且其发射非常依赖于介质。理论研究表明，金属-配体（M-二磷烷）到配体（L'，二亚胺）的跃迁，MLL'CT，负责产生发射特性的跃迁，但铜中心、碳硼烷簇、 1和2为二膦苯环。
更新日期：2021-12-06
中文翻译：
Closo- 或 Nido-Carborane Diphosphane 负责 [Cu(N^N)(P^P)]0/+ 中的强热致变色或时间激活延迟荧光 (TADF)
选择邻位或邻位碳硼烷二膦来制备杂配阳离子或中性 [Cu(N^N){(PPh 2 ) 2 C 2 B 10 H 10 }]PF 6 ( 1 ) 和 [Cu (N^N){(PPh 2 ) 2 C 2 B 9 H 10 }] ( 2 ) [N^N = 2-(4-噻唑基)苯并咪唑]。配合物1和2显示出非常不同的发射行为。中性复合物2表现出 TADF（时间激活延迟荧光），已作为粉末和 PMMA 复合材料进行研究，在两相中具有相似的 Δ E (S 1 – T 1 )、τ(T 1 ) 和 τ(S 1 )。阳离子配合物1表现出比2低得多的量子产率并且不显示TADF，但它表现出显着的热致变色发光，并且其发射非常依赖于介质。理论研究表明，金属-配体（M-二磷烷）到配体（L'，二亚胺）的跃迁，MLL'CT，负责产生发射特性的跃迁，但铜中心、碳硼烷簇、 1和2为二膦苯环。
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